催化学报 ›› 2021, Vol. 42 ›› Issue (8): 1297-1326.DOI: 10.1016/S1872-2067(20)63736-6
收稿日期:
2020-10-05
接受日期:
2020-11-29
出版日期:
2021-08-18
发布日期:
2020-12-10
基金资助:
Junwei Chen, Zuqiao Ou, Haixin Chen, Shuqin Song, Kun Wang, Yi Wang*()
Received:
2020-10-05
Accepted:
2020-11-29
Online:
2021-08-18
Published:
2020-12-10
Supported by:
摘要:
质子交换膜燃料电池(PEMFCs)因具有工作温度低、结构紧凑、无腐蚀、启动快和灵活性好等优点, 受到人们广泛关注. 但其工作时动力学迟缓且易受CO毒化影响, 往往需要负载Pt等贵金属催化剂, 导致PEMFCs的成本高昂, 阻碍了其商业化应用. 为提高Pt贵金属的利用率, 通常将Pt负载在载体材料上来提高Pt的分散性以减少Pt颗粒集聚, 因此, 合适的载体材料对于降低PEMFCs成本具有极大意义. 纳米碳材料由于具有高稳定性、可控的孔结构、可变的物理形态、可修饰的表面化学以及低成本等特点, 是一种理想的催化剂载体材料, 已被广泛应用于PEMFCs电催化剂中. 本文综述了PEMFCs电催化剂的纳米碳基载体的最新研究进展, 重点讨论了纳米碳的纳米结构和表面物理化学性质对电催化剂性能的影响, 主要从孔结构、杂原子掺杂以及功能性碳基载体方面对其进行概述. 在孔结构方面, 纳米碳载体的孔形貌和孔径大小能够显著地影响PEMFCs电催化剂的催化性能. 相比于无序孔, 有序孔能够减小反应物分子的传质阻力, 可使反应物分子更好地与载体孔道内的催化活性位点结合, 增加Pt催化剂的可及性, 从而提高反应活性. 合适的孔径不仅能够使纳米碳载体具有足够的传质通道, 还能提供充足的用于电催化反应的高比表面积, 从而增加电催化剂的催化性能. 在杂原子掺杂方面, 向纳米碳载体中掺入氮、硫和磷等杂原子能够稳定碳载体结构, 并增加载体表面与金属纳米粒子之间的结合位点, 提高金属纳米颗粒的分散性, 通过金属-载体之间的相互作用和协同作用提升电催化剂性能. 在功能性碳载体方面, 通过对纳米碳载体进行有针对性地改性得到具有特定功能的碳化物载体, 改性后的功能性碳化物载体能够通过加速CO反应中间体氧化以增加电催化剂的抗CO毒化能力, 并能够通过降低燃料电池腐蚀电流的方式提升电催化剂的耐久性.
本文讨论了纳米碳载体的最新进展, 指出PEMFC电催化剂载体的未来发展方向, 为PEMFC催化剂的未来研究和设计提供参考意见, 为推动PEMFC的市场化提供帮助.
陈军伟, 欧祖翘, 陈海鑫, 宋树芹, 王昆, 王毅. 电催化剂纳米碳基载体的研究进展[J]. 催化学报, 2021, 42(8): 1297-1326.
Junwei Chen, Zuqiao Ou, Haixin Chen, Shuqin Song, Kun Wang, Yi Wang. Recent developments of nanocarbon based supports for PEMFCs electrocatalysts[J]. Chinese Journal of Catalysis, 2021, 42(8): 1297-1326.
Nano carbon- based materials | Preparation methods | Material characteristics | Application fields | Problems to be solved as a catalyst support | Solutions | |||
---|---|---|---|---|---|---|---|---|
CNTs | 1. Arc discharge method 2. Laser ablation 3. Solid phase pyrolysis 4. Ion or laser sputtering 5. Catalytic cracking | 1. Hexagonal arrangement of carbon atom layers 2. One-dimensional nanostructure 3. Low impedance 4. Good conductivity and stability 5. Excellent resistance to electrochemical corrosion | 1. Composite materials 2. Electronic devices 3. Fluorescent labels | 1. Small active specific surface area 2. Surface inertness 3. High price | 1. Form hybrid materials with other carbon materials; 2. Dope metal or nonmetal to form composite materials | |||
Graphene (GP) | 1. Mechanical peeling 2. Redox method 3. Chemical vapor deposition (CVD) 4. Oriented epiphysis | 1. Two-dimensional planar structure 2. Large theoretical specific surface area (2630 m2 g-1) 3. High electrical conductivity (106 S cm-1) 4. Good resistance to electrochemical corrosion | 1. Physics 2. Materials 3. Electronic information 4. Computers | 1. Metal nanoparticles are easily reunited 2. Surface is chemically inert | 1. Structured into 3D material 2. Heteroatom doping 3. Surface defect engineering | |||
Ordered mesoporous carbon (OMC) | 1. Hard template method 2. Soft template method | 1. Uniformly adjustable pore diameter 2. Good conductivity 3. Good stability 4. Large specific surface area 5. Large pore volume | 1. Adsorption 2. Electrochemistry 3. Biology 4. Catalysis | 1. Complex manufacturing process 2. Orderly structure is easily broken | Surface functionalization with acid | |||
Carbon aerogel (CA) | 1. Organogel formation 2. Super-critical drying 3. Carbonization process | 1. Amorphous carbon materials 2. Controllable nanoporous 3D network structure 3. High specific surface area (600-1100 m2 g-1) 4. High porosity (80%-98%) 5. High stability | 1. Catalyst 2. Electrochemistry 3. Hydrogen storage 4. Template | 1. Low graphitization degree 2. Poor electrochemical corrosion resistance | 1. Surface modification 2. Improving the graphitization degree | |||
Carbon nanofiber (CNF) | 1. CVD 2. Solid phase synthesis 3. Electrospinning | 1. Large specific surface area 2. Good electrical conductivity 3. Good chemical stability 4. High single strength 5. Low cost | 1. Chemical engineering 2. Medicine 3. Sewage prevention | 1. Difficult to control shape 2. Uneven performance | 1. Surface stabilization 2. Element doping | |||
CB | 1. Spray method 2. Lamp smoke method 3. Drum method 4. Plasma method | 1. Good electrochemical performance 2. BET specific surface area is approximately 250 m2 g-1 3. The proportion of mesopores and macropores exceeds 54% 4. Electrical conductivity is approximately 2.77 S cm-1 | 1. Chemical engineering 2. Transportation 3. Textile | 1. Poor resistance to electrochemical corrosion 2. The proportion of micropores is still very high | 1. Improve the degree of graphitization 2. Doping heteroatoms |
Table 1 Nanocarbons as the support for PEMFC electrocatalysts.
Nano carbon- based materials | Preparation methods | Material characteristics | Application fields | Problems to be solved as a catalyst support | Solutions | |||
---|---|---|---|---|---|---|---|---|
CNTs | 1. Arc discharge method 2. Laser ablation 3. Solid phase pyrolysis 4. Ion or laser sputtering 5. Catalytic cracking | 1. Hexagonal arrangement of carbon atom layers 2. One-dimensional nanostructure 3. Low impedance 4. Good conductivity and stability 5. Excellent resistance to electrochemical corrosion | 1. Composite materials 2. Electronic devices 3. Fluorescent labels | 1. Small active specific surface area 2. Surface inertness 3. High price | 1. Form hybrid materials with other carbon materials; 2. Dope metal or nonmetal to form composite materials | |||
Graphene (GP) | 1. Mechanical peeling 2. Redox method 3. Chemical vapor deposition (CVD) 4. Oriented epiphysis | 1. Two-dimensional planar structure 2. Large theoretical specific surface area (2630 m2 g-1) 3. High electrical conductivity (106 S cm-1) 4. Good resistance to electrochemical corrosion | 1. Physics 2. Materials 3. Electronic information 4. Computers | 1. Metal nanoparticles are easily reunited 2. Surface is chemically inert | 1. Structured into 3D material 2. Heteroatom doping 3. Surface defect engineering | |||
Ordered mesoporous carbon (OMC) | 1. Hard template method 2. Soft template method | 1. Uniformly adjustable pore diameter 2. Good conductivity 3. Good stability 4. Large specific surface area 5. Large pore volume | 1. Adsorption 2. Electrochemistry 3. Biology 4. Catalysis | 1. Complex manufacturing process 2. Orderly structure is easily broken | Surface functionalization with acid | |||
Carbon aerogel (CA) | 1. Organogel formation 2. Super-critical drying 3. Carbonization process | 1. Amorphous carbon materials 2. Controllable nanoporous 3D network structure 3. High specific surface area (600-1100 m2 g-1) 4. High porosity (80%-98%) 5. High stability | 1. Catalyst 2. Electrochemistry 3. Hydrogen storage 4. Template | 1. Low graphitization degree 2. Poor electrochemical corrosion resistance | 1. Surface modification 2. Improving the graphitization degree | |||
Carbon nanofiber (CNF) | 1. CVD 2. Solid phase synthesis 3. Electrospinning | 1. Large specific surface area 2. Good electrical conductivity 3. Good chemical stability 4. High single strength 5. Low cost | 1. Chemical engineering 2. Medicine 3. Sewage prevention | 1. Difficult to control shape 2. Uneven performance | 1. Surface stabilization 2. Element doping | |||
CB | 1. Spray method 2. Lamp smoke method 3. Drum method 4. Plasma method | 1. Good electrochemical performance 2. BET specific surface area is approximately 250 m2 g-1 3. The proportion of mesopores and macropores exceeds 54% 4. Electrical conductivity is approximately 2.77 S cm-1 | 1. Chemical engineering 2. Transportation 3. Textile | 1. Poor resistance to electrochemical corrosion 2. The proportion of micropores is still very high | 1. Improve the degree of graphitization 2. Doping heteroatoms |
Fig. 4. (a) Schematic illustration for the effect of the structural regularity of the carbon support on the activity of Pt and (b) cyclic voltagrammograms of ethanol oxidation on Pt/WMCs and Pt/CMK-3. Reproduced with permission from Ref. [57], Copyright 2010 Elsevier. (c) Cyclic voltammetry curves of the as-prepared Pt/WMCs and Pt/CMK-3; (d) schematic diagram of highly OMC (CMK-3 and FDU-15) with different nanopore arrays and (e) comparison of electrochemical performance of Pt/CMK-3 and Pt/FDU-15. Reproduced with permission from Ref. [59], Copyright 2011 Royal Society of Chemistry.
Fig. 5. SEM (a), TEM (b), and HAADF-STEM (c,d) images of Fe/N-GPC; (e) Schematic diagram of molecular diffusion in an hierarchical pore structure. Reproduced with permission from Ref. [74], Copyright 2017 American Chemical Society.
Fig. 6. CV curve (a) and polarization curve (b) of Pt/WMC-F0 and Pt/WMC-F4; (c) Schematic of the effect of pore diameter of WMCs on the accessibility of Pt nanoparticles; (d) Comparison of the peak current density for EOR of mesoporous carbon with different pore diameters under different temperatures. Reproduced with permission from Ref. [78], Copyright 2010 Elsevier.
Fig. 8. (a) Schematic diagram of four types of N species in NCs, namely, pyridinic nitrogen (A), pyrrolic nitrogen (B), quaternary nitrogen (C), and pyridine-N-X (D); (b) Comparison of polarization curves; (c) Electrochemical performance of Pd/C, Pd@N-C NFs, and N-C NFs. Reproduced with permission from Ref. [97], Copyright 2019 Royal Society of Chemistry; (d) CV curves of Pt/NMC-1 and Pt/NMC-2 in an acid electrolyte. Reproduced with permission from Ref. [93], Copyright 2018 Elsevier.
Introduction method | Nanostructured morphology | N-precursor /method | T/°C | NAa /at% | N6b /% | N5c /% | NQd /% | NXe /% | ABET /m2 g-1 | ORR | R啊啊啊ef. | ||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
pH | Onset potential (V) | Limiting current density (mA cm-2) | |||||||||||
In situ process | N-CNTi | CCVDj | 1000 | 1.0 | 38.0 | 25.0 | √ | √ | 911.0 | 13.0 | — | — | [ |
N-Carbon nanocapsule | Gd-DTPAk carbonization | 700 | 7.1 | 27.6 | 61.8 | 8.4 | 2.2 | — | 13.0 | ~-0.95f,g | 20.1 | [ | |
900 | 3.2 | 19.8 | 63.3 | 7.2 | 5.3 | — | 13.0 | ~-0.95f,g | 17.6 | [ | |||
N-OMCl | Modified nanocasting | 800 | 5.07 | 31.9 | √ | √ | 9.0 | 470.0 | 13.0 | ~0.71h | 4.0 | [ | |
900 | 3.13 | 26.4 | √ | √ | 14.0 | 569.0 | 13.0 | ~0.75h | 4.3 | [ | |||
1000 | 2.20 | 20.9 | √ | √ | 18.5 | 629.0 | 13.0 | ~0.78h | 4.5 | [ | |||
1100 | 1.25 | 17.9 | √ | √ | 17.4 | 517.0 | 13.0 | ~0.73h | 4.0 | [ | |||
N-Nanoporous carbon | NaCl-assisted pyrolysis | 900 | 6.7 | 72.0 | 13.4 | 10.5 | 4.1 | 733.0 | 13.0 | 0.98g | 33.8 | [ | |
N-ZIFl derived carbon | N2+ carbonization | 700 | — | 52.0 | 32.0 | 11.0 | 5.0 | 74.47 | 1.0 | — | — | [ | |
750 | — | 46.0 | 27.0 | 16.0 | 11.0 | 75.81 | 1.0 | — | — | [ | |||
800 | — | 45.0 | 21.0 | 18.0 | 16.00 | 77.74 | 1.0 | — | — | [ | |||
850 | — | 42.0 | 21.0 | 19.0 | 17.0 | 79.43 | 1.0 | 0.58h | 4.75 | [ | |||
900 | — | 37.0 | 21.0 | 21.0 | 21.0 | 83.50 | 1.0 | — | — | [ | |||
N-mesoporous carbon | SiO2-assisted sol-gel method | 800 | 11.0 | 18.0 | 58.0 | — | 24.0 | 609.0 | 2.0 | ~0.80h | 1.44 | [ | |
800 | 6.0 | 12.0 | 61.0 | — | 27.0 | 736.0 | 2.0 | ~0.75h | 1.18 | [ | |||
Post treatment | N-GP | Flake graphite + NH3 heat treatment | 800 | 2.8 | 55.4 | 33.2 | 11.4 | — | — | 13.0 | 0.184g | ~2.7 | [ |
900 | 2.8 | 55.7 | 30.4 | 13.9 | — | — | 13.0 | 0.308g | ~2.9 | [ | |||
1000 | 2.0 | 51.0 | 33.0 | 16.0 | — | — | 13.0 | 0.204g | ~3.0 | [ | |||
N-OMC | NH3 heat treatment | 950 | 6.0 | 44.0 | — | 8.6 | — | 690.0 | 2.0 | 0.67h | ~3.7 | [ | |
1000 | 3.6 | 45.2 | — | 9.0 | — | 482.0 | 2.0 | 0.7h | ~4.0 | [ | |||
1050 | 4.6 | 46.9 | — | 10.0 | — | 229.0 | 2 | 0.72h | ~4.2 | [ | |||
N-MWCNTm | N2 plasma sputtering | — | 4.0 | 9.99 | 58.6 | 18.28 | 13.13 | — | 2.0 | 0.90h | 6.0 | [ | |
N-CNTi | CCVDj + NH3 heat treatment | 670 | 1.0 | 45.0 | 43.0 | 12.0 | — | 160.0 | 2.0 | 0.77h | 2.88 | [ |
Table 2 Metal free NC as electrocatalysts.
Introduction method | Nanostructured morphology | N-precursor /method | T/°C | NAa /at% | N6b /% | N5c /% | NQd /% | NXe /% | ABET /m2 g-1 | ORR | R啊啊啊ef. | ||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
pH | Onset potential (V) | Limiting current density (mA cm-2) | |||||||||||
In situ process | N-CNTi | CCVDj | 1000 | 1.0 | 38.0 | 25.0 | √ | √ | 911.0 | 13.0 | — | — | [ |
N-Carbon nanocapsule | Gd-DTPAk carbonization | 700 | 7.1 | 27.6 | 61.8 | 8.4 | 2.2 | — | 13.0 | ~-0.95f,g | 20.1 | [ | |
900 | 3.2 | 19.8 | 63.3 | 7.2 | 5.3 | — | 13.0 | ~-0.95f,g | 17.6 | [ | |||
N-OMCl | Modified nanocasting | 800 | 5.07 | 31.9 | √ | √ | 9.0 | 470.0 | 13.0 | ~0.71h | 4.0 | [ | |
900 | 3.13 | 26.4 | √ | √ | 14.0 | 569.0 | 13.0 | ~0.75h | 4.3 | [ | |||
1000 | 2.20 | 20.9 | √ | √ | 18.5 | 629.0 | 13.0 | ~0.78h | 4.5 | [ | |||
1100 | 1.25 | 17.9 | √ | √ | 17.4 | 517.0 | 13.0 | ~0.73h | 4.0 | [ | |||
N-Nanoporous carbon | NaCl-assisted pyrolysis | 900 | 6.7 | 72.0 | 13.4 | 10.5 | 4.1 | 733.0 | 13.0 | 0.98g | 33.8 | [ | |
N-ZIFl derived carbon | N2+ carbonization | 700 | — | 52.0 | 32.0 | 11.0 | 5.0 | 74.47 | 1.0 | — | — | [ | |
750 | — | 46.0 | 27.0 | 16.0 | 11.0 | 75.81 | 1.0 | — | — | [ | |||
800 | — | 45.0 | 21.0 | 18.0 | 16.00 | 77.74 | 1.0 | — | — | [ | |||
850 | — | 42.0 | 21.0 | 19.0 | 17.0 | 79.43 | 1.0 | 0.58h | 4.75 | [ | |||
900 | — | 37.0 | 21.0 | 21.0 | 21.0 | 83.50 | 1.0 | — | — | [ | |||
N-mesoporous carbon | SiO2-assisted sol-gel method | 800 | 11.0 | 18.0 | 58.0 | — | 24.0 | 609.0 | 2.0 | ~0.80h | 1.44 | [ | |
800 | 6.0 | 12.0 | 61.0 | — | 27.0 | 736.0 | 2.0 | ~0.75h | 1.18 | [ | |||
Post treatment | N-GP | Flake graphite + NH3 heat treatment | 800 | 2.8 | 55.4 | 33.2 | 11.4 | — | — | 13.0 | 0.184g | ~2.7 | [ |
900 | 2.8 | 55.7 | 30.4 | 13.9 | — | — | 13.0 | 0.308g | ~2.9 | [ | |||
1000 | 2.0 | 51.0 | 33.0 | 16.0 | — | — | 13.0 | 0.204g | ~3.0 | [ | |||
N-OMC | NH3 heat treatment | 950 | 6.0 | 44.0 | — | 8.6 | — | 690.0 | 2.0 | 0.67h | ~3.7 | [ | |
1000 | 3.6 | 45.2 | — | 9.0 | — | 482.0 | 2.0 | 0.7h | ~4.0 | [ | |||
1050 | 4.6 | 46.9 | — | 10.0 | — | 229.0 | 2 | 0.72h | ~4.2 | [ | |||
N-MWCNTm | N2 plasma sputtering | — | 4.0 | 9.99 | 58.6 | 18.28 | 13.13 | — | 2.0 | 0.90h | 6.0 | [ | |
N-CNTi | CCVDj + NH3 heat treatment | 670 | 1.0 | 45.0 | 43.0 | 12.0 | — | 160.0 | 2.0 | 0.77h | 2.88 | [ |
Fig. 9. Comparison of the relative potential surface energy of different types of N in nitrogen-doping graphitic carbon materials as calculated by DFT. Reproduced with permission from Ref. [104], Copyright 2020 American Chemical Society.
Fig. 10. Comparison of specific activity (a) and mass activity (b) of Pt/C and Pt@CNx/CNT before and after ADT. Reproduced with permission from Ref. [121], Copyright 2015 American Chemical Society.
Type of group | Name | Species released | Peak temperature (K) | |
---|---|---|---|---|
| Carboxylic | CO2 | ca. 510 | |
| Lactone | CO2 | ca. 940 | |
| Anhydride | CO + CO2 | ca. 820 | |
| Phenol | CO | ca. 905 | |
| Carbonyl | CO | ca. 1080 | |
| Ether | CO | ca. 973 | |
| Quinone | CO | ca. 1080 |
Table 3 Type of groups and their decomposition temperatures in the TPD test [147].
Type of group | Name | Species released | Peak temperature (K) | |
---|---|---|---|---|
| Carboxylic | CO2 | ca. 510 | |
| Lactone | CO2 | ca. 940 | |
| Anhydride | CO + CO2 | ca. 820 | |
| Phenol | CO | ca. 905 | |
| Carbonyl | CO | ca. 1080 | |
| Ether | CO | ca. 973 | |
| Quinone | CO | ca. 1080 |
Carbon materials | Oxidative treatment | Catalyst synthesis method | Untreated Pt particle (nm) | Treated Pt particle (nm) | Untreated electrochemical surface area (m2 g-1) | Treated electrochemical surface Area (m2 g-1) | R啊啊啊ef. |
---|---|---|---|---|---|---|---|
OMC | H2SO4:HNO3 (1:1) | Acid + refluxing + AEPTMSa | 4.3 | 2.9 | — | — | [ |
CB | HNO3:HCl (2:1) | Impregnation + H2 reduction | 2.7e | 3.5e | 63.0d 36.0e | 77.0b 34.9c | [ |
CS | Ozone | Heat treatment + 25 °C d | — | — | 24.4 | 2.9 | [ |
Heat treatment + 90 °C d | — | — | 24.4 | 11.1 | [ | ||
Heat treatment + 160 °C d | — | — | 24.4 | 87.1 | [ | ||
Heat treatment + 200 °C d | — | — | 24.4 | 18.7 | [ | ||
MWCNTe | KOH + calcination | EGf + microwave | 3.2 | 2.9 | 20.0 | 60.0 | [ |
H2SO4:HNO3 (3:1) | Plasma sputtering | 3.2d | 4.9d | 61.4 | 90.4 | [ | |
OH‒ | H2(PtCl6) + heat treatment | — | 2.4 | 79.0 | 58.0 | [ | |
COOH‒ | — | 2.6 | 79.0 | 73.0 | [ | ||
R-GOg | Ozone | High temperature adsorption | 2.0 | 3.0 | 48.0 | 51.0 | [ |
Fluorine | Soaking + freezing | 2.0 | 5.9 | 48.0 | 20.0 | [ |
Table 4 The effect of carbon support oxidative treatment on the electrocatalyst activity.
Carbon materials | Oxidative treatment | Catalyst synthesis method | Untreated Pt particle (nm) | Treated Pt particle (nm) | Untreated electrochemical surface area (m2 g-1) | Treated electrochemical surface Area (m2 g-1) | R啊啊啊ef. |
---|---|---|---|---|---|---|---|
OMC | H2SO4:HNO3 (1:1) | Acid + refluxing + AEPTMSa | 4.3 | 2.9 | — | — | [ |
CB | HNO3:HCl (2:1) | Impregnation + H2 reduction | 2.7e | 3.5e | 63.0d 36.0e | 77.0b 34.9c | [ |
CS | Ozone | Heat treatment + 25 °C d | — | — | 24.4 | 2.9 | [ |
Heat treatment + 90 °C d | — | — | 24.4 | 11.1 | [ | ||
Heat treatment + 160 °C d | — | — | 24.4 | 87.1 | [ | ||
Heat treatment + 200 °C d | — | — | 24.4 | 18.7 | [ | ||
MWCNTe | KOH + calcination | EGf + microwave | 3.2 | 2.9 | 20.0 | 60.0 | [ |
H2SO4:HNO3 (3:1) | Plasma sputtering | 3.2d | 4.9d | 61.4 | 90.4 | [ | |
OH‒ | H2(PtCl6) + heat treatment | — | 2.4 | 79.0 | 58.0 | [ | |
COOH‒ | — | 2.6 | 79.0 | 73.0 | [ | ||
R-GOg | Ozone | High temperature adsorption | 2.0 | 3.0 | 48.0 | 51.0 | [ |
Fluorine | Soaking + freezing | 2.0 | 5.9 | 48.0 | 20.0 | [ |
Fig. 11. Schematic diagram of H2SO4/HNO3, AEPTMS, and H2O2 oxidatively modifying the OMC surface. Reproduced with permission from Ref. [150], Copyright 2012 Elsevier.
Fig. 12. (a) Mass activity comparison of Pt/CB and Pt/CB_O before and after the ADT test; (b) Schematic diagram of the particle size changes of Pt/CB and Pt/CB_O during ADT. Reproduced with permission from Ref. [155], Copyright 2016 Elsevier.
Fig. 13. Schematic diagram of the structure and performance of the Pt/S-C catalyst. Reproduced with permission from Ref. [162], Copyright 2020 Elsevier.
Introduction method | Materials | Preparation methods | Particles size (nm) | pH value | Electrocatalytic performance | R啊啊啊ef. |
---|---|---|---|---|---|---|
In situ | S-carbon shell | Sodium dodecyl sulfate (SDS) + ethyleneglycol (EG)-stirring + pyrolysis | 8.39 | 13.0 | 0.99 c (vs. RHE) | [ |
S-nanocarbon spheres | Thioanisole (TOAS) + benzene-(solution plasma synthesis) | 3.00 | 13.0 | 490 d | [ | |
Post-treatment | S-graphene | GO + diethylene glycol methyl ether-refluxing | — | 13.0 | 0.02 c (vs. Hg/HgO) -0.105 e (vs. Hg/HgO) | [ |
GP + phenyl disulfide (PDS) + annealing | 4.00 | 2.0 | 182 d | [ | ||
S-CNTa | Functionalized CNTa + PDS-heating | 6.20 | 2.0 | 272 d 17.2f 1.61g | [ | |
S-MWCNTb | MWCNTs + SDS-ultrasonication 3,4-ethylenedioxythiophene + (NH4)2S2O8-annealing | 2.37 | 1.0 | 161.4f 0.16c | [ |
Table 5 Sulfur-doped carbon as the PEMFC electrocatalyst support.
Introduction method | Materials | Preparation methods | Particles size (nm) | pH value | Electrocatalytic performance | R啊啊啊ef. |
---|---|---|---|---|---|---|
In situ | S-carbon shell | Sodium dodecyl sulfate (SDS) + ethyleneglycol (EG)-stirring + pyrolysis | 8.39 | 13.0 | 0.99 c (vs. RHE) | [ |
S-nanocarbon spheres | Thioanisole (TOAS) + benzene-(solution plasma synthesis) | 3.00 | 13.0 | 490 d | [ | |
Post-treatment | S-graphene | GO + diethylene glycol methyl ether-refluxing | — | 13.0 | 0.02 c (vs. Hg/HgO) -0.105 e (vs. Hg/HgO) | [ |
GP + phenyl disulfide (PDS) + annealing | 4.00 | 2.0 | 182 d | [ | ||
S-CNTa | Functionalized CNTa + PDS-heating | 6.20 | 2.0 | 272 d 17.2f 1.61g | [ | |
S-MWCNTb | MWCNTs + SDS-ultrasonication 3,4-ethylenedioxythiophene + (NH4)2S2O8-annealing | 2.37 | 1.0 | 161.4f 0.16c | [ |
Fig. 14. (a) Schematic diagram for the preparation of the Pt/S-MWCNTs catalyst and (b,c) CV and current-time curves of Pt/S-MWCNT (A), Pt/AO-MWCNT (B), and commercial Pt/C (C) catalysts. Reproduced with permission from Ref. [166], Copyright 2017 Royal Society of Chemistry.
Introduction method | Material | Method | Metal particle size (nm) | pH | Catalytic performance | R啊啊啊ef. |
---|---|---|---|---|---|---|
In situ | N/S co-doped honeycomb-ordered carbon | 1. SiO2 template + fluidic ANTc cladding 2. Carbonization 3. HF etching | 2.6 | 1 | 100i (for ORR) 0.99j (for ORR) | [ |
N/S co-doped porous carbon | 1. Salt template method | 4.59 | 13 | 528k (for ORR) 112.34l (for ORR) ~0.8j (for ORR) | [ | |
Post treatment | N/P co-doped GP | 1. Phosphoric acid + GP -hydrothermal synthesis 2. NH4OH + P-GOd hydrothermal synthesis | 2-4 | 13 | 108.6m (for MOR) 133.5l (for MOR) | [ |
N/B co-doped SWCNHa | 1. B4C + melamine composites + carbon rod-DCe arc-vaporization | 5 | 1 | 100i (for ORR) | [ | |
S/P co-doped GP | 1. Phosphoric acid + GO (ultrasonication-calcination) 2. Sulfuric acid + P-GOd (ultrasonication-calcination) | 4.5 | 13 | 0.93i (for ORR) | [ | |
N-S-P co-doped HCSb | 1. HCCPf + BPSg + TEAh pyrolysis 2. Etching | 4-6 | 1 | 1127n (for EOR) 1.61o (for EOR) | [ |
Table 6 Multi-atom co-doped carbon as the PEMFC electrocatalyst support.
Introduction method | Material | Method | Metal particle size (nm) | pH | Catalytic performance | R啊啊啊ef. |
---|---|---|---|---|---|---|
In situ | N/S co-doped honeycomb-ordered carbon | 1. SiO2 template + fluidic ANTc cladding 2. Carbonization 3. HF etching | 2.6 | 1 | 100i (for ORR) 0.99j (for ORR) | [ |
N/S co-doped porous carbon | 1. Salt template method | 4.59 | 13 | 528k (for ORR) 112.34l (for ORR) ~0.8j (for ORR) | [ | |
Post treatment | N/P co-doped GP | 1. Phosphoric acid + GP -hydrothermal synthesis 2. NH4OH + P-GOd hydrothermal synthesis | 2-4 | 13 | 108.6m (for MOR) 133.5l (for MOR) | [ |
N/B co-doped SWCNHa | 1. B4C + melamine composites + carbon rod-DCe arc-vaporization | 5 | 1 | 100i (for ORR) | [ | |
S/P co-doped GP | 1. Phosphoric acid + GO (ultrasonication-calcination) 2. Sulfuric acid + P-GOd (ultrasonication-calcination) | 4.5 | 13 | 0.93i (for ORR) | [ | |
N-S-P co-doped HCSb | 1. HCCPf + BPSg + TEAh pyrolysis 2. Etching | 4-6 | 1 | 1127n (for EOR) 1.61o (for EOR) | [ |
Fig. 15. (a) Schematic diagram for the preparation of the Pd/N-P-G catalyst; (b) Comparison of CV curves of different catalysts in 1 M KOH; (c) Comparison chart of the ECSA values of different catalysts. Reproduced with permission from Ref. [170], Copyright 2019 Elsevier.
Introduction method | Synthesis product | Synthesis procedure | Nanostructured morphology | Surface area (m2 g-1) | Particle sizea (nm) | Electrocatalyst ratio for electrochemical reaction | R啊啊啊ef. |
---|---|---|---|---|---|---|---|
In situ process | WC-C | Hydrothermal carbonization | Microspheres | 256.0 | — | 1.4 for ESA 1.6 for ORRb,c | [ |
Hydrothermal carbonization | Mesoporous nanochain | 113.0 | — | 1.3 for ESA 1.6 for MORb | [ | ||
Hydrothermal carbonization | Hollow morphology | 433 | 3.6 | 1.96 for MORb | [ | ||
738 | — | 2.4 for MORb | |||||
Hydrothermal carbonization | Spherical morphology | 89 | 5.0 | 1.5 for ORRb | [ | ||
Soft templating carbonization | Ordered mesoporosity | 538.0 | 7.2 | 2.4 for MORd | [ | ||
WC-OMC | Hydrothermal and hard-templating carbonization | Ordered mesoporosity | 409.0 | 5.0 | 1.1 for MORd | [ | |
Pulse microwave-assisted polyol carbonization | Ordered mesoporosity | 409.0 | 5.0 | 1.0 for MORb | [ | ||
Hydrothermal carbonization | Ordered mesoporosity | 344.0 | 3.86 | — | [ | ||
Post-treatment | WC-C | Carbothermal H2 reduction | Bamboo-like morphology | — | — | 1.56 for MORb | [ |
Carbothermal N2 calcination | Macroporosity | 82.1 | 3.4 | 2.9 for ORRb | [ | ||
Carbothermal H2 reduction | Spherical morphology | 89.0 | 50.0-100.0 | — | [ | ||
WC-Ge | Microwave assisted carburization | Hexagonal prism shape | — | 5 | 2.29 for ESA | [ | |
WC-MWCNTf | Microwave carburization | Nanotube structure | — | — | 1.1 for MORb | [ | |
WC-GCg | Indirect carbonization | 3D Spheris | — | 50.0-200.0 | 3.7 for ORRa | [ | |
WC-HMGh | Microwave irradiation | Hemisphere-shaped macroporosity | 58.7 | 3.0 | 2.4 for ORRb | [ | |
WC-NCi | Indirect carbonization | Macroporosity | — | — | 2.5 for ORRb | [ |
Table 7 WC as electrocatalyst material supports.
Introduction method | Synthesis product | Synthesis procedure | Nanostructured morphology | Surface area (m2 g-1) | Particle sizea (nm) | Electrocatalyst ratio for electrochemical reaction | R啊啊啊ef. |
---|---|---|---|---|---|---|---|
In situ process | WC-C | Hydrothermal carbonization | Microspheres | 256.0 | — | 1.4 for ESA 1.6 for ORRb,c | [ |
Hydrothermal carbonization | Mesoporous nanochain | 113.0 | — | 1.3 for ESA 1.6 for MORb | [ | ||
Hydrothermal carbonization | Hollow morphology | 433 | 3.6 | 1.96 for MORb | [ | ||
738 | — | 2.4 for MORb | |||||
Hydrothermal carbonization | Spherical morphology | 89 | 5.0 | 1.5 for ORRb | [ | ||
Soft templating carbonization | Ordered mesoporosity | 538.0 | 7.2 | 2.4 for MORd | [ | ||
WC-OMC | Hydrothermal and hard-templating carbonization | Ordered mesoporosity | 409.0 | 5.0 | 1.1 for MORd | [ | |
Pulse microwave-assisted polyol carbonization | Ordered mesoporosity | 409.0 | 5.0 | 1.0 for MORb | [ | ||
Hydrothermal carbonization | Ordered mesoporosity | 344.0 | 3.86 | — | [ | ||
Post-treatment | WC-C | Carbothermal H2 reduction | Bamboo-like morphology | — | — | 1.56 for MORb | [ |
Carbothermal N2 calcination | Macroporosity | 82.1 | 3.4 | 2.9 for ORRb | [ | ||
Carbothermal H2 reduction | Spherical morphology | 89.0 | 50.0-100.0 | — | [ | ||
WC-Ge | Microwave assisted carburization | Hexagonal prism shape | — | 5 | 2.29 for ESA | [ | |
WC-MWCNTf | Microwave carburization | Nanotube structure | — | — | 1.1 for MORb | [ | |
WC-GCg | Indirect carbonization | 3D Spheris | — | 50.0-200.0 | 3.7 for ORRa | [ | |
WC-HMGh | Microwave irradiation | Hemisphere-shaped macroporosity | 58.7 | 3.0 | 2.4 for ORRb | [ | |
WC-NCi | Indirect carbonization | Macroporosity | — | — | 2.5 for ORRb | [ |
Fig. 17. (a) Schematic description for adsorbed CO on Pt and surface hydroxyls formed on WC with Pt/WC-C as the catalyst; (b) Schematic diagram of the preparation of the Pt@WC/OMC nanocomposite catalyst. Reproduced with permission from Ref. [200], Copyright 2015 Elsevier. (c) The MOR activity ratio between Pt/WC-C electrocatalysts with different surface areas and the commercial Pt/C.
Fig. 18. (a) ORR test curves of HMG/WC/Pt and Pt/C (1st and 2000th cycles); (b) Mass activity diagrams of HMG/WC/Pt and Pt/C; the CV curve of Pt/C (c) and HMG/WC/Pt (d) before and after 2000 cycles. Reproduced with permission from Ref. [191], Copyright 2016, Elsevier. a electrochemical surface area (m2 g-1), b limiting diffusion current (%), c mass activity (mA mgPt-1).
Fig. 19. (a) Comparison chart of the ECSA and current density of Pt/SiC and Pt/C single cells and (b) interface structure diagram of Pt/SiC and Pt/C electrodes before and after the AST test. Reproduced with permission from Ref. [223], Copyright 2017 Elsevier.
Functional carbide support | Catalyst synthesis method | T/oC | Pt particle size (nm) | ORR | Ref. | |
---|---|---|---|---|---|---|
pH | ECSAc/m2 gPt-1 | |||||
SiC | 1. Wood pyrolysis 2. Si and SiO2 calcination 3. Unreacted carbon separation 4. Acid washing | 1450 | — | 2.0 | 34d ; >80%e | [ |
TiC | — | — | 3.8 | 2.0 | 75d ; — | [ |
NbC | 1. ANOa + PVPb electrospinning 2. Calcination | 1100 | 3.1 | 13.0 | 43d ; 31%f | [ |
Table 9 Other functional carbides as the support for PEMFC electrocatalysts.
Functional carbide support | Catalyst synthesis method | T/oC | Pt particle size (nm) | ORR | Ref. | |
---|---|---|---|---|---|---|
pH | ECSAc/m2 gPt-1 | |||||
SiC | 1. Wood pyrolysis 2. Si and SiO2 calcination 3. Unreacted carbon separation 4. Acid washing | 1450 | — | 2.0 | 34d ; >80%e | [ |
TiC | — | — | 3.8 | 2.0 | 75d ; — | [ |
NbC | 1. ANOa + PVPb electrospinning 2. Calcination | 1100 | 3.1 | 13.0 | 43d ; 31%f | [ |
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